Sterically hindered amines

ABSTRACT

An intermediate of the formula (I) wherein the radicals R 1  are independently of one another methyl, ethyl or n-propyl, is suitable for preparing a compound of the formula (A) wherein X is a group of the formula (A-I) or (A-II), Y is C 11 -C 17 alkyl, and Z is a direct bond, —(CH 2 ) 8 — or —CH 2 —S—CH 2 —. The compounds of the formula (A) are useful for stabilizing an organic material against thermal, oxidative or light induced degradation.

The present invention relates to intermediates which are useful for thepreparation of stabilizers, to the preparation of said intermediates andto the light stabilizers prepared with said intermediates as well as toan organic material containing the stabilizers and to a method forstabilizing an organic material.

In more detail, the present invention relates to an intermediate of theformula (I)

wherein the radicals R₁ are independently of one another methyl, ethylor n-propyl, preferably n-propyl.

A further embodiment of the present invention is a process for thepreparation of an intermediate of the formula (I)

wherein R₁ is methyl, ethyl or n-propyl;which comprises reacting a compound of the formula (I-a)

with ammonia in an organic solvent in the presence of hydrogen andplatinum as hydrogenation catalyst.

Examples of suitable organic solvents are alcohols such as methanol,ethanol, propanol, isopropanol, butanol and the like; and (C₁-C₄alkyl)esters such as ethyl acetate; and the like. A C₁-C₄alcohol or a(C₁-C₄alkyl) ester is preferred.

A hydrogen pressure of 1 to 60 bar, in particular 1 to 30 bar, ispreferred.

The reaction temperature is for example 20° to 120° C., preferably 20°to 100° C., in particular 40° to 70° C.

The catalyst platinum is preferably supported by a carrier material.Examples of suitable catalyst support are zeolite Y, inorganic oxidesuch as silica, alumina, or silica-alumina graphite or activatedcharcoal. Further examples of the carrier are metal aluminates, such ascalcium aluminate, magnesium aluminate, barium hexyluminate, nickelaluminate, and alumina, silica, silica-alumina, activated carbon, ceria,zirconia, chromia-alumina, titania, magnesium oxide, and mixturesthereof.

Platinum on carbon is the preferred hydrogenation catalyst.

The amount of the hydrogenation catalyst is in particular 0.1 to 10%,for example 1 to 5%, by weight, relative to the weight of the compoundof the formula (I-a).

The hydrogenation catalyst is preferably added in two portions.

The molar ratio of ammonia to the compound of the formula (I-a) ispreferably 0.5/2 to 1.3/2, in particular 1/2.

The compounds of the formula (I-a) are known and can be prepared inanalogy to known processes, e.g. as described in WO-A-2008/003,602 andWO-A-2008/003,605.

A further embodiment of the present invention relates to a compound ofthe formula (A), which can be prepared by using one of the abovedescribed intermediates of the formula (I),

wherein X is a group of the formula (A-I) or (A-II),

Y is C₁₁-C₁₇alkyl,Z is a direct bond, —(CH₂)₈— or —CH₂—S—CH₂—, andthe radicals R₁ are independently of one another methyl, ethyl orn-propyl, in particular n-propyl.

Preferred examples of C₁₁-C₁₇alkyl are —C₁₁H₂₃-n and —C₁₇H₃₅-n.

The light stabilizers of the formula (A) have an excellent thermalstability.

A further embodiment of the present invention is a compositioncontaining

a) an organic material, preferably a natural or synthetic organicpolymer, and

b) a compound of the formula (A) as defined above.

Examples of component a) are

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).        2. Mixtures of the polymers mentioned under 1), for example        mixtures of polypropylene with polyisobutylene, polypropylene        with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of        different types of polyethylene (for example LDPE/HDPE).        3. Copolymers of monoolefins and diolefins with each other or        with other vinyl monomers, for example ethylene/propylene        copolymers, linear low density polyethylene (LLDPE) and mixtures        thereof with low density polyethylene (LDPE),        propylene/but-1-ene copolymers, propylene/isobutylene        copolymers, ethylene/but-1-ene copolymers, ethylene/hexene        copolymers, ethylene/methylpentene copolymers, ethylene/heptene        copolymers, ethylene/octene copolymers,        ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin        copolymers (e.g. ethylene/norbornene like COC),        ethylene/1-olefins copolymers, where the 1-olefin is generated        in-situ; propylene/butadiene copolymers, isobutylene/isoprene        copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl        acrylate copolymers, ethylene/alkyl methacrylate copolymers,        ethylene/vinyl acetate copolymers or ethylene/acrylic acid        copolymers and their salts (ionomers) as well as terpolymers of        ethylene with propylene and a diene such as hexadiene,        dicyclopentadiene or ethylidene-norbornene; and mixtures of such        copolymers with one another and with polymers mentioned in 1)        above, for example polypropylene/ethylenepropylene copolymers,        LDPE/ethylene-vinyl acetate copolymers (EVA),        LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA,        LLDPE/EAA and alternating or random polyalkylene/carbon monoxide        copolymers and mixtures thereof with other polymers, for example        polyamides.        4. Hydrocarbon resins (for example C₅-C₉) including hydrogenated        modifications thereof (e.g. tackifiers) and mixtures of        polyalkylenes and starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).17. Polyureas, polyimides, polyamide-imides, polyetherimides,polyesterimides, polyhydantoins and polybenzimidazoles.18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones or lactides, forexample polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalateand polyhydroxybenzoates as well as copolyether esters derived fromhydroxyl-terminated polyethers, and also polyesters modified withpolycarbonates or MBS. Copolyesters may comprise, for example—but arenot limited to—polybutylenesuccinate/terephtalate,polybutyleneadipate/terephthalate,polytetramethyleneadipate/terephthalate, polybutylensuccinate/adipate,polybutylensuccinate/carbonate, poly-3-hydroxybutyrate/octanoatecopolymer, poly-3-hydroxybutyrate/hexanoate/decanoate terpolymer.Furthermore, aliphatic polyesters may comprise, for example—but are notlimited to—the class of poly(hydroxyalkanoates), in particular,poly(propiolactone), poly(butyrolactone), poly(pivalolactone),poly(valerolactone) and poly(caprolactone), polyethylenesuccinate,polypropylenesuccinate, polybutylenesuccinate,polyhexamethylenesuccinate, polyethyleneadipate, polypropyleneadipate,polybutyleneadipate, polyhexamethyleneadipate, polyethyleneoxalate,polypropyleneoxalate, polybutyleneoxalate, polyhexamethyleneoxalate,polyethylenesebacate, polypropylenesebacate, polybutylenesebacate andpolylactic acid (PLA) as well as corresponding polyesters modified withpolycarbonates or MBS. The term “polylactic acid (PLA)” designates ahomo-polymer of preferably poly-L-lactide and any of its blends oralloys with other polymers; a co-polymer of lactic acid or lactide withother monomers, such as hydroxy-carboxylic acids, like for exampleglycolic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid,4-hydroxy-valeric acid, 5-hydroxy-valeric acid, 6-hydroxy-caproic acidand cyclic forms thereof; the terms “lactic acid” or “lactide” includeL-lactic acid, D-lactic acid, mixtures and dimers thereof, i.e.L-lactide, D-lactide, meso-lacide and any mixtures thereof.19. Polycarbonates and polyester carbonates.20. Polyketones.21. Polysulfones, polyether sulfones and polyether ketones.22. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.23. Drying and non-drying alkyd resins.24. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.25. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.26. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.28. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.29. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, PQM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.30. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.31. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

The organic material is preferably a synthetic polymer, in particularfrom one of the above groups. A polyolefin homo- or copolymer ispreferred. Polyethylene, polypropylene, a polyethylene copolymer or apolypropylene copolymer are particularly preferred.

Of interest is also ethylene/propylene/diene elastomer (EPDM).

The compound of the formula (A) may be present in the organic materialin an amount of preferably 0.005 to 5%, in particular 0.01 to 1% or 0.05to 1%, relative to the weight of the organic material.

The stabilizer of the formula (A) can be incorporated into the organicmaterial to be stabilized by known methods, for example before or duringshaping or by applying the dissolved or dispersed stabilizer to theorganic material, if necessary with subsequent evaporation of thesolvent. The stabilizer can be added to the organic material in the formof a powder, granules or a masterbatch, which contains said stabilizerin, for example, a concentration of from 2.5 to 25% by weight.

The materials stabilized according to this invention can be used in awide variety of forms, for example as films, fibres, tapes, mouldingcompositions, profiles or as binders for paints, adhesives or putties.

Examples of Processing or Transformation of the Plastics According tothe Present Invention are:

Injection blow molding, extrusion, blow molding, rotomolding, in molddecoration (back injection), slush molding, injection molding,co-injection molding, forming, compression molding, pressing, filmextrusion (cast film; blown film), fiber spinning (woven, nonwoven),drawing (uniaxial, biaxial), annealing, deep drawing, calandering,mechanical transformation, sintering, coextrusion, coating, lamination,crosslinking (radiation, peroxide, silane), vapor deposition, weldtogether, glue, vulkanization, thermoforming, pipe extrusion, profileextrusion, sheet extrusion; sheet casting, spin coating, strapping,foaming, recycling/rework, extrusion coating, visbreaking (peroxide,thermal), fiber melt blown, spunbonded, surface treatment (coronadischarge, flame, plasma), sterilization (by gamma rays, electronbeams), cast polymerization (R&M process, RAM extrusion), gel-coating,tape extrusion, GMT-process, SMC-process, plastisol, and dipping (PVC,latex).

The Plastics According to the Present Invention May be Used for thePreparation of:

I-1) Floating devices, marine applications, pontoons, buoys, plasticlumber for decks, piers, boats, kayaks, oars, and beach reinforcements.

I-2) Automotive applications, in particular bumpers, dashboards,battery, rear and front linings, moldings parts under the hood, hatshelf, trunk linings, interior linings, air bag covers, electronicmoldings for fittings (lights), panes for dashboards, headlamp glass,instrument panel, exterior linings, upholstery, automotive lights, headlights, parking lights, rear lights, stop lights, interior and exteriortrims; door panels; gas tank; glazing front side; rear windows; seatbacking, exterior panels, wire insulation, profile extrusion forsealing, cladding, pillar covers, chassis parts, exhaust systems, fuelfilter/filler, fuel pumps, fuel tank, body side mouldings, convertibletops, exterior mirrors, exterior trim, fasteners/fixings, front endmodule, glass, hinges, lock systems, luggage/roof racks, pressed/stampedparts, seals, side impact protection, sound deadener/insulator andsunroof.I-3) Road traffic devices, in particular sign postings, posts for roadmarking, car accessories, warning triangles, medical cases, helmets,tires.I-4) Devices for plane, railway, motor car (car, motorbike) includingfurnishings.I-5) Devices for space applications, in particular rockets andsatellites, e.g. reentry shields.I-6) Devices for architecture and design, mining applications, acousticquietized systems, street refuges, and shelters.II-1) Appliances, cases and coverings in general and electric/electronicdevices (personal computer, telephone, handy, printer, television-sets,audio and video devices), flower pots, satellite TV bowl, and paneldevices.II-2) Jacketing for other materials such as steel or textiles.II-3) Devices for the electronic industry, in particular insulation forplugs, especially computer plugs, cases for electric and electronicparts, printed boards, and materials for electronic data storage such aschips, check cards or credit cards.II-4) Electric appliances, in particular washing machines, tumblers,ovens (microwave oven), dish-washers, mixers, and irons.II-5) Covers for lights (e.g. street-lights, lamp-shades).II-6) Applications in wire and cable (semi-conductor, insulation andcable-jacketing).II-7) Foils for condensers, refrigerators, heating devices, airconditioners, encapsulating of electronics, semi-conductors, coffeemachines, and vacuum cleaners.III-1) Technical articles such as cogwheel (gear), slide fittings,spacers, screws, bolts, handles, and knobs.III-2) Rotor blades, ventilators and windmill vanes, solar devices,swimming pools, swimming pool covers, pool liners, pond liners, closets,wardrobes, dividing walls, slat walls, folding walls, roofs, shutters(e.g. roller shutters), fittings, connections between pipes, sleeves,and conveyor belts.III-3) Sanitary articles, in particular shower cubicles, lavatory seats,covers, and sinks.III-4) Hygienic articles, in particular diapers (babies, adultincontinence), feminine hygiene articles, shower curtains, brushes,mats, tubs, mobile toilets, tooth brushes, and bed pans.III-5) Pipes (cross-linked or not) for water, waste water and chemicals,pipes for wire and cable protection, pipes for gas, oil and sewage,guttering, down pipes, and drainage systems.III-6) Profiles of any geometry (window panes) and siding.III-7) Glass substitutes, in particular extruded plates, glazing forbuildings (monolithic, twin or multiwall), aircraft, schools, extrudedsheets, window film for architectural glazing, train, transportation,sanitary articles, and greenhouse.III-8) Plates (walls, cutting board), extrusion-coating (photographicpaper, tetrapack and pipe coating), silos, wood substitute, plasticlumber, wood composites, walls, surfaces, furniture, decorative foil,floor coverings (interior and exterior applications), flooring, duckboards, and tiles.III-9) Intake and outlet manifolds.III-10) Cement-, concrete-, composite-applications and covers, sidingand cladding, hand rails, banisters, kitchen work tops, roofing, roofingsheets, tiles, and tarpaulins.IV-1) Plates (walls and cutting board), trays, artificial grass,astroturf, artificial covering for stadium rings (athletics), artificialfloor for stadium rings (athletics), and tapes.IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienicarticles/geotextiles/monofilaments; filters; wipes/curtains(shades)/medical applications), bulk fibers (applications such asgown/protection clothes), nets, ropes, cables, strings, cords, threads,safety seat-belts, clothes, underwear, gloves; boots; rubber boots,intimate apparel, garments, swimwear, sportswear, umbrellas (parasol,sunshade), parachutes, paraglides, sails, “balloon-silk”, campingarticles, tents, airbeds, sun beds, bulk bags, and bags.IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps,ponds, dumps, walls roofing membranes, geomembranes, swimming pools,curtains (shades)/sun-shields, awnings, canopies, wallpaper, foodpacking and wrapping (flexible and solid), medical packaging (flexible &solid), airbags/safety belts, arm- and head rests, carpets, centreconsole, dashboard, cockpits, door, overhead console module, door trim,headliners, interior lighting, interior mirrors, parcel shelf, rearluggage cover, seats, steering column, steering wheel, textiles, andtrunk trim.V) Films (packaging, dump, laminating, agriculture and horticulture,greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, wastebags, wallpaper, stretch film, raffia, desalination film, batteries, andconnectors.VI-1) Food packing and wrapping (flexible and solid), BOPP, BOPET,bottles.VI-2) Storage systems such as boxes (crates), luggage, chest, householdboxes, pallets, shelves, tracks, screw boxes, packs, and cans.VI-3) Cartridges, syringes, medical applications, containers for anytransportation, waste baskets and waste bins, waste bags, bins, dustbins, bin liners, wheely bins, container in general, tanks forwater/used water/chemistry/gas/oil/gasoline/diesel; tank liners, boxes,crates, battery cases, troughs, medical devices such as piston,ophthalmic applications, diagnostic devices, and packing forpharmaceuticals blister.VII-1) Extrusion coating (photo paper, tetrapack, pipe coating),household articles of any kind (e.g. appliances, thermos bottle/clotheshanger), fastening systems such as plugs, wire and cable clamps,zippers, closures, locks, and snap-closures.VII-2) Support devices, articles for the leisure time such as sports andfitness devices, gymnastics mats, ski-boots, inline-skates, skis, bigfoot, athletic surfaces (e.g. tennis grounds); screw tops, tops andstoppers for bottles, and cans.VII-3) Furniture in general, foamed articles (cushions, impactabsorbers), foams, sponges, dish clothes, mats, garden chairs, stadiumseats, tables, couches, toys, building kits (boards/figures/balls),playhouses, slides, and play vehicles.VII-4) Materials for optical and magnetic data storage.VII-5) Kitchen ware (eating, drinking, cooking, storing).VII-6) Boxes for CD's, cassettes and video tapes; DVD electronicarticles, office supplies of any kind (ball-point pens, stamps andink-pads, mouse, shelves, tracks), bottles of any volume and content(drinks, detergents, cosmetics including perfumes), and adhesive tapes.VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives,structural adhesives, food boxes (fruit, vegetables, meat, fish),synthetic paper, labels for bottles, couches, artificial joints (human),printing plates (flexographic), printed circuit boards, and displaytechnologies.VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin),wollastonite, pigments, carbon black, T102, mica, nanocomposites,dolomite, silica, silicates, glass, asbestos).

The stabilized material may additionally also contain variousconventional additives, for example:

1. Antioxidants 1.1. Alkylated Monophenols

For example 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols

For example 2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-didodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and Alkylated Hydroquinones

For example 2,6-di-tert-butyl-4-methoxyphenol,2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone,2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyphenyl stearate,bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols

For example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol andmixtures thereof (vitamin E).

1.5. Hydroxylated Thiodiphenyl Ethers

For example 2, 2′-thiobis(6-tert-butyl-4-methylphenol),2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols

For example 2, 2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-Benzyl Compounds

For example 3, 5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated Malonates

For exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic Hydroxybenzyl Compounds

For example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetra methylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds

For example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxpnilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates

For example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols

For example 4-hydroxylauranilide, 4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid

With mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid

With mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid

With mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid

With mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid

E.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard® XL-1, supplied by Uniroyal).

1.18. Ascorbic Acid (vitamin C) 1.19. Aminic Antioxidants

For example N,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-secbutyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tertoctylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allyiphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.

2. UV Absorbers and Light Stabilizers 2.1.2-(2′-Hydroxyphenyl)benzotriazoles

For example 2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300;

where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones

For example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy,4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of Substituted and Unsubstituted Benzoic Acids

For example 4-tert-butylphenyl salicylate, phenyl salicylate,octylphenyl salicylate, dibenzoyl resorcinol,bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol,2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates

For example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-pmethoxycinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate,N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyltetra(α-cyano-β,β-diphenylacrylate.

2.5. Nickel Compounds

For example nickel complexes of2,2′-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically Hindered Amines

For example carbonic acidbis(1-undecyloxy-2,2,6,6-tetramethyl-4-piperidyl)ester,bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2;2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine,2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor(Clariant; CAS Reg. No. 106917-31-1],5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, thereaction product of2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine),1,3,5-tris(N-cyclohexylN-(2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino)-s-triazine,1,3,5-tris(N-cyclohexylN-(1,2,2,6,6-pentamethylpiperazine-3-one-4-yl)amino)-s-triazine.

2.7. Oxamides

For example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxydisubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines

For example 2, 4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{(2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine.

3. Metal Deactivators

For example N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine,N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and Phosphonites

For example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkylphosphites, tris(nonylphenyl) phosphite, trilauryl phosphite,trioctadecyl phosphite, distearytpentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tertbutylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos® 168, Ciba SpecialtyChemicals Inc.), tris(nonylphenyl) phosphite,

5. Hydroxylamines

For example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine,N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine,N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones

For example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone,N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecyInitrone,N-tetradecyl-alphatridecylnnitrone, N-hexadecyl-alpha-pentadecyInitrone,N-octadecyl-alpha-heptadecyInitrone,N-hexadecyl-alpha-heptadecyInitrone,N-ocatadecyl-alpha-pentadecyInitrone,N-heptadecyl-alpha-heptadecyInitrone, N-octadecyl-alphahexadecyInitrone,nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenatedtallow amine.

7. Thiosynergists

For example dilauryl thiodipropionate, dimistryl thiodipropionate,distearyl thiodipropionate or distearyl disulfide.

8. Peroxide Scavengers

For example esters of β-thiodipropionic acid, for example the lauryl,stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zincsalt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate,dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide Stabilizers

For example copper salts in combination with iodides and/or phosphoruscompounds and salts of divalent manganese.

10. Basic Co-Stabilizers

For example melamine, polyvinylpyrrolidone, dicyandiamide, triallylcyanurate, urea derivatives, hydrazine derivatives, amines, polyamides,polyurethanes, alkali metal salts and alkaline earth metal salts ofhigher fatty acids, for example calcium stearate, zinc stearate,magnesium behenate, magnesium stearate, sodium ricinoleate and potassiumpalmitate, antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleating Agents

For example inorganic substances, such as talcum, metal oxides, such astitanium dioxide or magnesium oxide, phosphates, carbonates or sulfatesof, preferably, alkaline earth metals; organic compounds, such as mono-or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoicacid, adipic acid, diphenylacetic acid, sodium succinate or sodiumbenzoate; polymeric compounds, such as ionic copolymers (ionomers).Especially preferred are 1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and Reinforcing Agents

For example calcium carbonate, silicates, surface treated silica (asdescribed e.g. in US-A-2007/60,697 and US-A-2009/111,918), glass fibres,glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxidesand hydroxides, carbon black, graphite, wood flour and flours or fibersof other natural products, synthetic fibers.

13. Other Additives

For example plasticisers, lubricants, emulsifiers, pigments, rheologyadditives, catalysts, flow-control agents, optical brighteners,flameproofing agents, anti-static agents and blowing agents.

14. Benzofuranones and Indolinones

For example those disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No.4,338,244; U.S. Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat.No. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839,EP-A-0591102; EP-A-1291384 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tertbutylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tertbutylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.

The weight ratio of the compound of the formula (A) to the total amountof the conventional additives can be, for example, 100:1 to 1:1000 or10:1 to 1:100 or 10:1 to 1:10.

A further embodiment of the present invention is a method forstabilizing an organic material against degradation induced by light,heat or oxidation, which comprises incorporating a compound of theformula (A) as defined above into the organic material.

Another embodiment of the present invention is the use of a compound ofthe formula (A) as defined above for stabilizing an organic materialagainst thermal, oxidative or light induced degradation.

The compounds of the formula (A) are also useful as flame retardants.

The following examples illustrate the invention in greater detail. Allpercentages and parts are by weight, unless stated otherwise.

EXAMPLE I-1: PREPARATION OF THE INTERMEDIATE OF THE FORMULA (I-1)

In a steel autoclave 600 g of1-propoxy-2,2,6,6-tetramethyl-piperidin-4-one in 1000 ml of methanol areslowly added to 230 ml of methanolic ammonia (10% solution in methanol)and 12 g of Pt-catalyst (5% on C) under 60° C./10 bar hydrogenatmosphere. After 16 h of hydrogenation, 12 g of Pt-catalyst and 50 g of1-propoxy-2,2,6,6-tetramethyl-piperidin-4-one are added and furtherhydrogenated for 21 h. After filtration of the catalyst and removal ofthe solvent from the filtrate, 575 g of grey crystals are obtained. Thecrude product is recrystallized from 500 ml of methanol. The desiredintermediate is obtained in form of colorless crystals.

Yield: 68.7% of theory

Melting point: 67-69° C.

Mass Spectroscopy (Chemical Ionization) (=MS (Cl)): 412 (MH+)

EXAMPLE I-2: PREPARATION OF THE INTERMEDIATE OF THE FORMULA (I-2)

The intermediate is prepared from1-ethoxy-2,2,6,6-tetramethyl-piperidin-4-one and ammonia in analogy toEXAMPLE I-1. After recrystallization of the crude product from methanol,the desired intermediate is obtained in the form of off-white crystals.

Yield: 63.1%

Melting point: 104-106° C.

MS (Cl): 384 (MH⁺)

EXAMPLE I-3: PREPARATION OF THE INTERMEDIATE OF THE FORMULA (I-3)

The intermediate is prepared from1-methoxy-2,2,6,6-tetramethyl-piperidin-4-one in analogy to EXAMPLE I-1.After recrystallization of the crude product from methanol, the desiredintermediate is obtained in the form of off-white crystals.

Yield: 53%

Melting point: 74-76° C.

MS (Cl): 356 (MH⁺)

EXAMPLE A-1: PREPARATION OF THE COMPOUND OF THE FORMULA (A-1)

26 g (77 mmol) of stearoyl chloride is added at 0-5° C. to a solution of30.4 g (74 mmol) of the intermediate (I-1), 9.32 g of triethylamine, 90mg of 4-dimethylaminopyridine in 370 ml of toluene. The filtrate of thisreaction mixture is extracted with water, saturated sodium bicarbonateand water. After standard work-up of the organic phase (drying andremoval of the solvent at the rotary evaporator), the desired compoundis obtained as an amorphous yellowish solid.

Yield: 44.8 g (89.6% of theory)

IR(neat): 1650 (Amide I)

MS (Cl): 678 (MH⁺)

EXAMPLE A-2: PREPARATION OF THE COMPOUND OF THE FORMULA (A-2)

N,N-bis(1-propoxy-2,2,6,6-tetramethylpiperidine-4-yl)lauric acid amideis prepared from lauroyl chloride and the intermediate (I-1) in analogyto Example A-1. The desired compound is obtained as a yellow viscousoil.

Yield: 93.5%

IR (neat): 1649 (Amide I)

MS (Cl): 594 (MH⁺)

EXAMPLE A-3: PREPARATION OF THE COMPOUND OF THE FORMULA (A-3)

N,N-bis(1-ethoxy-2,2,6,6-tetramethylpiperidine-4-yl)stearic acid amideis prepared from stearoyl chloride and the intermediate (I-2) in analogyto EXAMPLE (A-1). After purification by flash chromatography onsilicagel (eluent hexane/ethyl acetate 5:1) the desired compound isobtained as a yellowish amorphous solid.

Yield: 100%

IR (neat): 1649 (Amide I)

MS (Cl): 650 (MH⁺)

EXAMPLE A-4: PREPARATION OF THE COMPOUND OF THE FORMULA (A-4)

N,N-bis(1-methoxy-2,2,6,6-tetramethylpiperidine-4-yl)stearic acid isprepared from stearoyl chloride and the intermediate (A-3) in analogy toEXAMPLE (A-1). After purification by flash chromatography on silicagel(eluent hexane/ethyl acetate 4:1), the desired compound is obtained as ayellowish oil.

Yield: 72.7%

IR (neat): 1650 (Amide I)

MS (Cl): 622 (MH⁺)

EXAMPLE A-5: PREPARATION OF THE COMPOUND OF THE FORMULA (A-5)

N,N,N′,N′-Tetrakis(1-propoxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacicacid diamide is prepared from 26.52 mmol of sebacic acid dichloride and50.52 mmol of the intermediate (I-1) in analogy to Example (A-1)(solvent methylene chloride). The desired compound is obtained as anamorphous solid.

Yield: 94.7%.

Melting point: 68-75° C.

IR (neat): 16476 (Amide I)

MS (Cl): 990 (MH⁺).

EXAMPLE A-6: PREPARATION OF THE COMPOUND OF THE FORMULA (A-6)

N,N,N′,N′-Tetrakis(1-propoxy-2,2,6,6-tetramethylpiperidine-4-yl)oxamideis prepared from oxalyl chloride and the intermediate (A-1) in analogyto EXAMPLE (A-5). After recrystallization from methanol, the desiredcompound is obtained as a colorless solid.

Yield: 78%

Melting point: 249-250° C.

IR (neat): 1654, 1637 (Amide I)

MS (Cl): 977 (MH⁺)

EXAMPLE A-7: PREPARATION OF THE COMPOUND OF THE FORMULA (A-7)

N,N,N′,N′-Tetrakis(1-propoxy-2,2,6,6-tetramethylpiperidine-4-yl)-thiodiglycollicacid diamide is prepared from thiodiglycollic acid dichloride and theintermediate (A-1) in analogy to EXAMPLE (A-5). After purification byflash chromatography on silicagel (eluent hexane/ethyl acetate 1:1) thedesired compound is obtained as an amorphous yellowish solid.

Yield: 77.6%

Melting point: 90-96° C.

IR (neat): 1643 (Amide I)

MS (Cl): 938 MH⁺

EXAMPLE B: STABILIZATION OF ETHYLENE/PROPYLENE/DIENE ELASTOMER (EPDM)

One part of the stabilizer indicated in Table 1 is incorporated into anEPDM based formulation containing the following components:

100 parts by weight of EPDM,

1 part by weight of stearic acid,

5 parts by weight of ZnO,

3.4 parts by weight of polyethylene glycol,

60 parts by weight of paraffin oil,

90 parts by weight of kaolin,

180 parts by weight of chalk,

1 part by weight of sulfur,

2.5 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide,

1 part by weight of Zn dibutyl dithiophosphate.

The formulation is treated on a two-roll mill at 120° C. for 5 minutes.

From the formulation obtained, 2 mm thick samples are prepared in apress at 175° C. and 180 bar with 10 minutes curing time.

The obtained samples are weathered according to ISO 4892-2 with drycycle only. The formation of cracks and the level of chalking areoptically assessed with a magnifying glass.

The results are listed in the following table.

TABLE 1 Stabilizer Chalking Cracks None Strong chalking 2 Compound ofEXAMPLE A-1 No chalking 0-1 Compound of EXAMPLE A-2 Low chalking 0-1Compound of EXAMPLE A-5 Low chalking 0-1 Compound of EXAMPLE A-6 Lowchalking 0-1 0: no cracks 3: surface fully cracked

EXAMPLE C: THERMAL STABILITY

The thermal stability is determined by Differential Scanning calorimetry(DSC). The measurements are carried out in a Mettler Toledo® DSC 30machine. Approx. 10 mg of the compound of EXAMPLE A-6 is weighted into astandard DSC aluminum pan (40 microliter). The pan is sealed with analuminium lid and punctured with a fine needle. Then, the pan isinserted in the oven and kept under nitrogen during the experiment. Thethermal behaviour of the test sample is recorded in the temperaturerange of 30-500° C. using a heating rate of 10° C./min. The experimentaldata are analyzed using Mettler Toledo® STARe software (V 9.01) todetermine the onset temperature of the sample decomposition. The firstexothermic peak of the DSC curve is indicated in Table 2 below.

TABLE 2 Stabilizer DSC first exothermic peak (N₂) [° C.] Compound ofEXAMPLE A-6 314.2

The invention claimed is:
 1. A compound of the formula (A-5)


2. A composition containing a) an ethylene/propylene/diene elastomer andb) 0.005 to 5% relative to the weight of the ethylene/propylene/dieneelastomer, of a compound of the formula A-5 as defined in claim 1.